US3867408A - 1,2-Epoxy-2-methyl-6-heptanone ketals - Google Patents

1,2-Epoxy-2-methyl-6-heptanone ketals Download PDF

Info

Publication number
US3867408A
US3867408A US283111A US28311172A US3867408A US 3867408 A US3867408 A US 3867408A US 283111 A US283111 A US 283111A US 28311172 A US28311172 A US 28311172A US 3867408 A US3867408 A US 3867408A
Authority
US
United States
Prior art keywords
methyl
epoxy
ketal
heptanone
ketals
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US283111A
Inventor
Hans K Dietl
Kent C Brannock
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US283111A priority Critical patent/US3867408A/en
Application granted granted Critical
Publication of US3867408A publication Critical patent/US3867408A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/32—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by aldehydo- or ketonic radicals

Definitions

  • isophytol is reacted with trimethyl hydroquinone or dimethyl hydroquinone under acid conditions to form the desired product.
  • isophytol has also been found useful in the synthesis of vitamin K.
  • Isophytol has been prepared by reacting 2-methyl-6-keto-heptanal with geranyl halide in a Wittig reaction, the resulting product hydrogenated to phytone which is reacted with a vinyl Grignard reagent in water to produce isophytol.
  • lchikawa and Kato Bulletin of Chemical Society oflapan 41, 1232 (1968).
  • 1,2-Epoxy-Z-methyl-6-heptanone ketals in accordance with this invention are intermediates in a process for producing 6-oxo-2-methylheptanal ketals.
  • the above compounds the ketal is selected from the groups alkyl, substituted or unsubstituted cycloalkyl, aryl, alkylene or substituted alkylene.
  • the substituents' may be lower alkyl, aryl or cycloalkyl groups.
  • alkyl any aliphatic hydrocarbon radical derived by dropping one hydrogen from an alkanc and having from 1 to 10 carbon atoms.
  • Alkylene means any aliphatic hydrocarbon radical derived by dropping two hydrogens from an alkane and having from 2 to 4 carbon atoms and lower alkyl substituted alkylene means any alkylene as defined above having 2 to 4 carbon atoms any of which may have a lower alkyl substituent.
  • a cycloalkyl is a substituted or unsubstituted 5-7 carbon ring structive hydrocarbon.
  • lower alkyl is meant a hydrocarbon having from 1 to 5 carbon atoms.
  • Ary'l means a molecule having an aromatic nucleus at least one carbon of which has a lower alkyl substituent.
  • the ring formed when R and R are -A has no more than seven members.
  • Suitable alcohols which can be utilized in this reaction include methanol, ethanol, n-propyl alcohol. isopropyl alcohol. n-butyl alcohol, sec-butyl alcohol, and other aliphatic alcohols up to and including decanol. These include also lower alkyl substituted aliphatic alcohols.
  • the compound 1,2-epoxy-2-methyl-6-heptanone alkyl ketal can also be prepared by reaction with ethyl orthoformate as described in Fieser and Fieser, Advanced OrganicChemistry (New York, 1961) p. 442.
  • 1,2-Epoxy-2-methyl-6-heptanone aryl ketal is prepared as described above except the alcohol or mixture of alcohols used include a ring compound having a lower alkyl substituent.
  • examples of such alcohols include benzyl alcohol, oz-ethylbenzyl alcohol, w-ethylbenzyl alcohol, and benzylpropyl alcohol.
  • 1,2-Epoxy-2-methyl-6-heptanone cycloalkyl ketal is produced in the manner described above but utilizing a cyclo-alcohol such as cyclohexanol, cyclopentanol, cycloheptanol and these alcohols with alkyl substituents.
  • alkyl, aryl and cycloalkyl alcohols may also be used.
  • the resulting compound can be an alkylaryl ketal and/or an alkyl-cycloalkyl ketal and/or an aryl-cycloalkyl ketal.
  • suitable peracids include perbenzoic, monoperphthalic, perpropionic, perbutyric. permonochloracetic, peracetic performic, perisovaleric, percrotonic, diperoxalic, percamphoric, trifluoroperacetic, p-nitroperbenzoic, mchloroperbenzoic acids. Epoxidation can also be achieved by the use of hydrogen peroxide.
  • l,2-Epoxy-2-methyl-6-heptanone cyclic alkylene or lower alkyl substituted cyclic alkylene ketal is produced by reacting 2-methyl-1-hepten-6-one with a diol having from 2 to 4 carbon atoms or with a lower alkyl substituted diol having from 2 to 4 carbon atoms.
  • the compound produced as a result of this reaction is 2-methyl-1-hepten-6-one cyclic alkylene or lower alkyl substituted cyclic alkylene ketal.
  • This compound is reacted with a peracid or peroxide as described above.
  • the resulting 'product is 1,2-epoxy-2-methyl-6- heptanone cyclic alkylene or lower alkyl substituted cyclic alkylene ketal.
  • Suitable glycols include ethylene glycol, 1,2- propylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 2,3-butylene glycol and these glycols with lower alkyl. aryl or cycloalkyl substituents. Suitable peracids and peroxides are given above.
  • a ketal by the reaction of a ketone and an alcohol is known. See, for example, Fieser and Fieser, op. cit., pp. 441443.
  • the epoxidation of a compound at a double bond utilizing a peracid or a peroxide is also known. See Weissberger, Helerocyclic Compounds. Part 1 (New York, 1964) pp. 31-93.
  • reaction mixture is allowed to warm to room temperature over a period of 4 hours, stirred for one hour at room temperature, and then poured into water.
  • the organic layer is separated, dried over MgSO. and filtered. Distillation gives l,2-epoxy-2-methyl-6-heptanone cyclic ethylene ketal (179 g., corresponding to a yield of 90%), having a boiling point of 7678C. at 1 mm.
  • EXAMPLE 2 EXAMPLE 3 The exact procedure of Example 1 is repeated except 1,2-propanediol is used instead of ethylene glycol. Distillation gives l,2-epoxy-2-methyl-6-heptanone cyclic methylethylene ketal at a yield of 90%.
  • EXAMPLE 7 The exact procedure of Example 1 is repeated except a mixture of n-propyl alcohol with n-butyl alcohol is used instead of ethylene glycol. Distillation gives a mixture of l,2-epoxy-2-methyl-6-heptanone propyl ketal; l,2-epoxy-2-methyl-6-heptanone propyl butyl ketal, and l,2-epoxy-2-methyl-6-heptanone butyl ketal.
  • R and R taken together are A wherein A- is alkylene having 2 to 4 carbon atoms or alkylene having 2 to 4 carbon atoms substituted with alkyl having 1 to 5 carbon atoms, cycloalkyl having a 57 carbon ring structure or phenyl one carbon of which is substituted with alkyl having 1 to. 5 carbon atoms.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Compounds (AREA)

Abstract

1,2-Epoxy-2-methyl-6-heptanone ketals, intermediates in the synthesis of isophytol.

Description

United States Patent Dietl et a1.
[ Feb. 18, 1975 l,Z-EPOXY-2-METHYL-6-HEPTANONE KETALS Inventors: Hans K. Dietl; Kent C. Brannock,
both of Kingsport, Tenn.
Eastman Kodak Company, Rochester, NY.
Filed: Aug. 23, 1972 Appl. No.: 283,111
Assignee:
US. Cl 260/340.9, 260/338, 260/340.7,
260/348 R, 424/278 Int. Cl C07d 13/04 Field of Search 260/3409, 348 R, 3407,
Primary Examiner-Donald G. Daus Assistant ExaminerJames H. Turnipseed Attorney, Agent, or FirmJohn F. Stevens; Cecil D. Quillen, Jr,
[57] ABSTRACT 1,2-Epoxy-Z-methyl-6-heptan0ne ketals, intermediates in the synthesis of isophytol.
5 Claims, N0 Drawings l,2-EPOXY-Z-METHYL-tS-HEPTANONE KETALS This invention relates to 1,2-epoxy-2-methyl-6- heptanone ketals which are intermediates in a process for the manufacture of isophytol.
In the synthesis of dl-tocopherols, isophytol is reacted with trimethyl hydroquinone or dimethyl hydroquinone under acid conditions to form the desired product. See US Pat. No. 2,411,969 of Karrer. Isophytol has also been found useful in the synthesis of vitamin K. Isophytol has been prepared by reacting 2-methyl-6-keto-heptanal with geranyl halide in a Wittig reaction, the resulting product hydrogenated to phytone which is reacted with a vinyl Grignard reagent in water to produce isophytol. See lchikawa and Kato, Bulletin of Chemical Society oflapan 41, 1232 (1968).
In this reaction the key starting material is Z-methyl- 6'ketoheptanal.
It has been found that 6-oxo-2-methylheptanal ketals are simpler to use in the Wittig reaction than 2-methyl-6-keto-heptanal since the keto group is protected as the ketal. This leaves only the aldehyde group to react in the Wittig reaction.
1,2-Epoxy-Z-methyl-6-heptanone ketals in accordance with this invention are intermediates in a process for producing 6-oxo-2-methylheptanal ketals.
1n the above compounds the ketal is selected from the groups alkyl, substituted or unsubstituted cycloalkyl, aryl, alkylene or substituted alkylene. The substituents'may be lower alkyl, aryl or cycloalkyl groups.
By alkyl is meant any aliphatic hydrocarbon radical derived by dropping one hydrogen from an alkanc and having from 1 to 10 carbon atoms. Alkylene means any aliphatic hydrocarbon radical derived by dropping two hydrogens from an alkane and having from 2 to 4 carbon atoms and lower alkyl substituted alkylene means any alkylene as defined above having 2 to 4 carbon atoms any of which may have a lower alkyl substituent. A cycloalkyl is a substituted or unsubstituted 5-7 carbon ring structive hydrocarbon. By lower alkyl is meant a hydrocarbon having from 1 to 5 carbon atoms. Ary'l means a molecule having an aromatic nucleus at least one carbon of which has a lower alkyl substituent.
This compound can also be defined with reference to the following structural formula:
R R2 Ha (I) X) egg; -(CH2) Qc-cHs wherein R and R are either the same or different alkyl, cycloalkyl or aryl groups having 1 to carbon atoms or R and R taken together are A- wherein -A is an alkylene group having 2 to 4 carbon atoms, or A is a lower alkyl I to 5 carbon atoms), aryl or cycloalkyl substituted alkylene group having 2 to 4 carbon atoms. The ring formed when R and R are -A has no more than seven members.
In preparing 1,2-epoxy-2-methyl-6-heptanone alkyl ketal, 2-methyl-1-hepten-6-one prepared from isobutylene, acetone and formaldehyde described in British Pat. No. 1,178,036 is reacted with an aliphatic alcohol having from 1 to 10 carbon atoms or a mixture of such alcohols. The product of this reaction is 2-methy1-1- hepten-o-one alkyl ketal which is then epoxidized by reaction with a peracid or peroxide. The resulting product is l,2-epoxy-2-methyl--heptanone alkyl ketal.
Suitable alcohols which can be utilized in this reaction include methanol, ethanol, n-propyl alcohol. isopropyl alcohol. n-butyl alcohol, sec-butyl alcohol, and other aliphatic alcohols up to and including decanol. These include also lower alkyl substituted aliphatic alcohols.
The compound 1,2-epoxy-2-methyl-6-heptanone alkyl ketal can also be prepared by reaction with ethyl orthoformate as described in Fieser and Fieser, Advanced OrganicChemistry (New York, 1961) p. 442.
1,2-Epoxy-2-methyl-6-heptanone aryl ketal is prepared as described above except the alcohol or mixture of alcohols used include a ring compound having a lower alkyl substituent. Examples of such alcohols include benzyl alcohol, oz-ethylbenzyl alcohol, w-ethylbenzyl alcohol, and benzylpropyl alcohol.
1,2-Epoxy-2-methyl-6-heptanone cycloalkyl ketal is produced in the manner described above but utilizing a cyclo-alcohol such as cyclohexanol, cyclopentanol, cycloheptanol and these alcohols with alkyl substituents.
Mixtures of alkyl, aryl and cycloalkyl alcohols may also be used. The resulting compound can be an alkylaryl ketal and/or an alkyl-cycloalkyl ketal and/or an aryl-cycloalkyl ketal.
In forming the epoxide suitable peracids include perbenzoic, monoperphthalic, perpropionic, perbutyric. permonochloracetic, peracetic performic, perisovaleric, percrotonic, diperoxalic, percamphoric, trifluoroperacetic, p-nitroperbenzoic, mchloroperbenzoic acids. Epoxidation can also be achieved by the use of hydrogen peroxide.
l,2-Epoxy-2-methyl-6-heptanone cyclic alkylene or lower alkyl substituted cyclic alkylene ketal is produced by reacting 2-methyl-1-hepten-6-one with a diol having from 2 to 4 carbon atoms or with a lower alkyl substituted diol having from 2 to 4 carbon atoms. The compound produced as a result of this reaction is 2-methyl-1-hepten-6-one cyclic alkylene or lower alkyl substituted cyclic alkylene ketal. This compoundis reacted with a peracid or peroxide as described above. The resulting 'product is 1,2-epoxy-2-methyl-6- heptanone cyclic alkylene or lower alkyl substituted cyclic alkylene ketal.
Suitable glycols include ethylene glycol, 1,2- propylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 2,3-butylene glycol and these glycols with lower alkyl. aryl or cycloalkyl substituents. Suitable peracids and peroxides are given above.
The formation of a ketal by the reaction of a ketone and an alcohol is known. See, for example, Fieser and Fieser, op. cit., pp. 441443. The epoxidation of a compound at a double bond utilizing a peracid or a peroxide is also known. See Weissberger, Helerocyclic Compounds. Part 1 (New York, 1964) pp. 31-93.
The following examples are presented for a. further understanding of the invention.
EXAMPLE 1 ml.) is collected in a Dean-Stark trap over a period of 7 hours. The reaction mixture is poured into 1,500 ml.
water, the water layer washed with 200 ml. benzene, the organic layers combined, dried over MgSO, and filtered. Distillation of the resulting filtered product gives Z-methyl-l-hepten-fi-one ethylene ketal (204 g. corresponding to a 78% yield) at 80-86C., 110 mm. The 2-methyl-l-hepten-6-one ethylene ketal (200 g.) is dissolved in methylene chloride (800 ml. sodium acetate (65 g.) is added, and the mixture cooled to C. Peracetic acid (40%, 240 g.) containing sodium acetate (8 g.) is added with stirring over a period of l hour. The reaction mixture is allowed to warm to room temperature over a period of 4 hours, stirred for one hour at room temperature, and then poured into water. The organic layer is separated, dried over MgSO. and filtered. Distillation gives l,2-epoxy-2-methyl-6-heptanone cyclic ethylene ketal (179 g., corresponding to a yield of 90%), having a boiling point of 7678C. at 1 mm.
EXAMPLE 2 EXAMPLE 3 The exact procedure of Example 1 is repeated except 1,2-propanediol is used instead of ethylene glycol. Distillation gives l,2-epoxy-2-methyl-6-heptanone cyclic methylethylene ketal at a yield of 90%.
EXAMPLE 4 The exact procedure of Example 1 is repeated except n-propyl alcohol is used instead of ethylene glycol. Distillation gives l,2-epoxy-2-methyl-6-heptanone dipropyl ketal at a yield of 90%.
EXAMPLE 5 The exact procedure of Example 1 is repeated except benzyl alcohol is used instead of ethylene glycol. Distillation gives l,2-epoxy-2-methyl-6-heptanone dibenzyl ketal.
EXAMPLE 6 The exact procedure of Example 1 is repeated except cyclohexanol is used instead of ethylene glycol. Distillation gives l,2-epoxy-2-methyl-o-heptanone dicyclohexyl ketal.
EXAMPLE 7 The exact procedure of Example 1 is repeated except a mixture of n-propyl alcohol with n-butyl alcohol is used instead of ethylene glycol. Distillation gives a mixture of l,2-epoxy-2-methyl-6-heptanone propyl ketal; l,2-epoxy-2-methyl-6-heptanone propyl butyl ketal, and l,2-epoxy-2-methyl-6-heptanone butyl ketal.
Disclosed herein are new compounds, 1,2-epoxy-2- methyl-6-heptanone ketals including alkyl, aryl, cyclic alkylene, lower alkyl substituted cyclic or cycloalkyl alkylene ketals. These compounds are valuable intermediates in the production of phytol and isophytol which are reactants in the synthesis of dl-tocopherols, i.e., Vitamin E.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
I claim:
1. A ketal having the formula 1 3 Ha v (CH2) :5 -Cl-la wherein R and R are the same or different alkyl having 1 to 10 carbon atoms, cycloalkyl having 5 to 7 carbon ring structure or phenyl one carbon atom of which has an alkyl having 1 to 5 carbon atoms; or
R and R taken together are A wherein A- is alkylene having 2 to 4 carbon atoms or alkylene having 2 to 4 carbon atoms substituted with alkyl having 1 to 5 carbon atoms, cycloalkyl having a 57 carbon ring structure or phenyl one carbon of which is substituted with alkyl having 1 to. 5 carbon atoms.
2. A ketal according to claim 1 wherein R and R are -A and the ring formed thereby has no more than 7 members.
3. l,2-Epoxy-2-methyl-6-heptanone cyclic ethylene ketal having the formula I CH2 2 a, ll :(CHE) rkE CHe 4. l,2-Epoxy-2-methyl-6-heptanone cyclic methylethylene ketal.
5. 1,2-Epoxy-2-methyl-6-heptanone dipropyl ketal. =l

Claims (5)

1. A KETAL HAVING THE FORMULA
2. A ketal according to claim 1 wherein R1 and R2 are -A- and the ring formed thereby has no more than 7 members.
3. 1,2-Epoxy-2-methyl-6-heptanone cyclic eThylene ketal having the formula
4. 1,2-Epoxy-2-methyl-6-heptanone cyclic methylethylene ketal.
5. 1,2-Epoxy-2-methyl-6-heptanone dipropyl ketal.
US283111A 1972-08-23 1972-08-23 1,2-Epoxy-2-methyl-6-heptanone ketals Expired - Lifetime US3867408A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US283111A US3867408A (en) 1972-08-23 1972-08-23 1,2-Epoxy-2-methyl-6-heptanone ketals

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US283111A US3867408A (en) 1972-08-23 1972-08-23 1,2-Epoxy-2-methyl-6-heptanone ketals

Publications (1)

Publication Number Publication Date
US3867408A true US3867408A (en) 1975-02-18

Family

ID=23084572

Family Applications (1)

Application Number Title Priority Date Filing Date
US283111A Expired - Lifetime US3867408A (en) 1972-08-23 1972-08-23 1,2-Epoxy-2-methyl-6-heptanone ketals

Country Status (1)

Country Link
US (1) US3867408A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050065380A1 (en) * 2002-01-14 2005-03-24 Addisseo France S.A.S. Process for the preparation of phytone

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3117982A (en) * 1959-10-07 1964-01-14 Fritzsche Brothers Inc 6-substittuted ionones and methods and intermediates used in their production
US3136788A (en) * 1961-07-17 1964-06-09 Shell Oil Co Glycidyl glycidate and the preparation of epoxyalkyl esters of epoxyalkanoic acids from epoxyalkanals

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3117982A (en) * 1959-10-07 1964-01-14 Fritzsche Brothers Inc 6-substittuted ionones and methods and intermediates used in their production
US3136788A (en) * 1961-07-17 1964-06-09 Shell Oil Co Glycidyl glycidate and the preparation of epoxyalkyl esters of epoxyalkanoic acids from epoxyalkanals

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050065380A1 (en) * 2002-01-14 2005-03-24 Addisseo France S.A.S. Process for the preparation of phytone
US6987203B2 (en) 2002-01-14 2006-01-17 Adisseo France S.A.S. Process for the preparation of phytone

Similar Documents

Publication Publication Date Title
US4851585A (en) Vitamin E intermediates
US3867408A (en) 1,2-Epoxy-2-methyl-6-heptanone ketals
US4097531A (en) Substituted cyclopropane process and product
US3922287A (en) Polyene compounds
US3878200A (en) Aryl substituted tertiary carbinols
US3859310A (en) 6-oxo-2-methylheptanal ketals
Henrick et al. The chemistry of the euphorbiaceae—XI: The diterpenes of ricinocarpus muricatus and the stereochemistry of eperuic acid
Goldsmith et al. Preparation and rearrangement of trichothecane-like compounds. Synthesis of aplysin and filiformin
US3426046A (en) Synthesis of epoxides from allylic sulfonium salts
US4261907A (en) Stereospecific process
HOSHINO et al. Synthesis of Sceletium and Amaryllidaceae alkaloids,(±)-mesembrine and (±)-dihydromaritidine,(±)-epidihydromaritidine,(±)-elwesine, and (±)-epielwesine
JPS642109B2 (en)
US3558658A (en) 2h,5h-pyrano(3,2-e)(1)benzo-pyran-4(3h),5-diones
US3140296A (en) Production of dioxane derivatives
Kabuto et al. The Synthesis and the Stereochemistry of 4-Chromanones and 4-Chromanols with Bulky Substituents
US3624105A (en) Method for synthesizing rhodoxanthin
US2421770A (en) Acetal compounds
US4594456A (en) Racemic and optically active 3-hydroxy-alpha-cyclocitral, its acetals and optically active 3-oxo-alpha-cyclocitral acetals, and their preparation
US3824291A (en) 4-(3-hydroxy-1,5-dimethylhex-1-yl)-1-cyclohexene-1-carboxaldehyde
US4808736A (en) Process for the preparation of hydroquinone derivatives and d-α-tocopherol
Reinaud et al. Synthesis of new 3-(-2-alkenyl)-2-hydroxy-5-methoxy-p-benzoquinones via Claisen rearrangement of original 5-methoxy-4-(2-propenyloxy)-o-benzoquinones
Smeets et al. Cyclopropanation reactions with α, β-epoxy diazomethyl ketones and rearrangement of α, β-epoxy cyclopropyl ketones
US3641156A (en) Juvabione and derivatives thereof
Yates et al. The photodimerization of 3-phenyl-2-cyclohexenone
US4568759A (en) Preparation of epoxides